LEAN NOx TRAP/CONVERSION CATALYST

ABSTRACT

A process and composition for converting nitrogen oxides present in exhaust gases produced by an internal combustion engine utilize cobalt and at least one alkali metal or alkaline earth metal as a component of an adsorbent. The process involves contacting the exhaust gas with an adsorbent which adsorbs the nitrogen oxides in lean-burn conditions and recurrently reducing the oxygen concentration of the exhaust gas. During such periods of reduced oxygen concentration, the nitrogen oxides are then desorbed and reduced to nitrogen, thereby reducing the concentration of the nitrogen oxides in the exhaust gas. The composition of the adsorbent comprises an oxide support and at least two components loaded on the support and containing cobalt and at least one alkali metal or alkaline earth metal. The composition demonstrates improved activity at higher temperatures and improved thermal stability.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. patentapplication Ser. No. 10/878,240, filed Jun. 28, 2004, which is adivisional application of U.S. patent application Ser. No. 09/956,424,filed Sep. 19, 2001, the disclosures of both of which are incorporatedherein by reference.

FIELD OF THE INVENTION

The present invention relates to improvements in emission control forpartial lean-burn vehicle engines. In particular, the present inventionis directed to the emission control of nitrogen oxides from exhaust gasof internal combustion engines, including diesel engines.

BACKGROUND OF THE INVENTION

Exhaust gases from vehicle engines primarily contain carbon oxides (COand CO₂), nitrogen oxides (NO_(x)), hydrocarbons, sulfur dioxide, andsoot. At present, one of the most significant problems is removal ofnitrogen oxides, NO_(x), which are produced during high temperaturecombustion. In the case of “lean-burn” or partial lean-burn engines, inwhich there is an excess of oxygen in the exhaust gases, the reductionof NO_(x) to N₂ is particularly difficult because reducing components inthe exhaust are often completely consumed by the oxygen that is presentin large excess.

Catalysts are employed in the exhaust systems of automotive vehicles toconvert CO, CO₂, hydrocarbons, and NO_(x), produced during engineoperation into more desirable gases. When the engine is operated in astoichiometric air/fuel ratio, catalysts containing palladium, platinumor rhodium, also known as “three way catalysts,” are able to efficientlyconvert all the gases simultaneously. However, when the engine isoperated in “lean-burn” conditions, to realize a benefit in fueleconomy, such three way catalysts are able to convert CO andhydrocarbons, but are not efficient in the reduction of NO_(x).

Previous attempts to develop a Lean NO_(x) Catalyst (LNC) that willselectively catalyze NO_(x) reduction by HC's has met with limitedsuccess. Catalyst materials developed to date that catalyze theHC—NO_(x) reaction allow only about 30 to 50% NO_(x) conversion underconditions of interest. These catalysts are usually either platinum (Pt)group metals (PGM) containing materials that function only at lowtemperatures (150-200° C.) or base metal materials that function athigher temperatures (300-600° C.). The LNC approach on its own, however,is not sufficient to achieve acceptable NO_(x) reduction to allow futurelegislated limits to be achieved.

Certain alkali or alkaline earth metals such as potassium or strontiumin combination with platinum are capable of storing or adsorbingnitrogen oxides under lean conditions, or in conditions of excessoxygen. More specifically, the platinum first oxidizes NO to NO₂ and theNO₂ subsequently forms a nitrate complex with the alkali or alkalineearth material. For simplicity herein, this sequence of reactions andadsorption shall be referred to as nitrogen oxides being adsorbed, eventhough NO is not adsorbed but is actually first converted to NO₂ whichis then adsorbed. In a rich environment caused, for example, by aregeneration pulse, the nitrate is thermodynamically unstable and thestored NO_(x) is released. The NO_(x) then, with the aid of a catalyst,reacts with reducing species in the exhaust gas to form N₂. Theseadsorbents are known as Lean NO_(x) Trap catalysts (LNT).

Some shortcomings have been identified for the LNT approach. First, alimited operating temperature window exists for the LNT. As withthree-way catalysts, a minimum temperature is required for NO_(x)adsorption and conversion. However, unlike the three-way catalysts,NO_(x) adsorption and conversion decreases with increasing temperatureabove a certain temperature (usually about 350 to 400° C.), due todecreasing stability of the adsorbed nitrate. A second shortcoming ofthe LNT is the high cost due to the use of platinum group metals.

There remains a need for improved NO_(x) conversion catalysts forautomotive lean-burn operation emissions.

SUMMARY OF THE INVENTION

The present invention pertains to a process and composition whichconverts nitrogen oxides present in exhaust gas produced by an internalcombustion engine. The composition of an adsorbent of the presentinvention comprises an oxide support and at least two components loadedon the oxide support and containing cobalt and at least one alkali metalor alkaline earth metal. The most preferred alkali metal is potassium,however other alkali metals may be used, such as cesium. The componentsmay include additional constituents, such as platinum group metals, butin some cases may be used without any additional constituents. Theprocess comprises the steps of contacting the exhaust gas containingnitrogen oxides with an adsorbent of the present invention, where theadsorbent adsorbs the nitrogen oxides in lean-burn conditions, and thenrecurrently reducing the oxygen concentration of the exhaust gas. Thereduction in oxygen concentration is done in a manner to causedesorption of the nitrogen oxides and reduction of the nitrogen oxidesin the exhaust gas to nitrogen.

In a preferred embodiment of the present invention, the process alsoincludes contacting the exhaust gases with a catalyst such as a platinumgroup metal, before or while contacting the exhaust gases with theadsorbent. This step may be performed in order to increase theconversion of the nitrogen oxides in the exhaust gas. The selectedcatalyst or the platinum group metal may be deposited on the oxidesupport with the adsorbent, but is preferably disposed on the upstreamside of the oxide support.

The present invention is also directed to an exhaust system forconverting nitrogen oxides present in exhaust gas provided by an engine.The system includes an upstream catalyst and a downstream catalyst. Theupstream catalyst may be a three way catalyst, a lean NO_(x) catalyst,or an oxidation catalyst. The downstream catalyst is a lean NO_(x) trapof the present invention.

It is understood that both the foregoing general description and thefollowing detailed description are exemplary, but not restrictive, ofthe invention.

BRIEF DESCRIPTION OF THE DRAWINGS

The FIGURE is a graph showing nitrogen oxide conversion of thecobalt-potassium trap (also referred to herein as an “adsorbent”) alongwith comparative examples.

DETAILED DESCRIPTION OF THE INVENTION

The present invention pertains to a process and composition whichconverts nitrogen oxides present in exhaust gas produced by an internalcombustion engine. The phrase converting nitrogen oxides means that atleast some, and preferably almost all, of the nitrogen oxides enteringthe catalyst are converted to nitrogen. The present invention is alsodirected to an internal combustion engine exhaust gas catalyst systemcomprising a nitrogen oxide trap (LNT) (also referred to herein as an“adsorbent”), and the process of converting NO_(x) in exhaust gases fromthe engine.

The process for converting nitrogen oxides present in exhaust gasesproduced by an internal combustion engine first comprises the step ofcontacting the exhaust gas containing nitrogen oxides with an adsorbentof the present invention capable of adsorbing the nitrogen oxides inlean-burn conditions. The lean burn conditions involve an excess ofoxygen, which is typical in exhaust gases. The adsorbent then stores theNO_(x) during the conditions of excess oxygen. When the exhaust flowinginto the LNT is lean (i.e. high oxygen content), NO in the exhaust iscatalytically oxidized to NO₂ and then stored by the adsorbent as anitrate salt.

The second step of the present process comprises recurrently reducingthe oxygen concentration of the exhaust gas in a manner to causedesorption of the nitrogen oxides and reduction of the nitrogen oxidesin the exhaust gas to nitrogen. Reducing the oxygen concentration in theexhaust gas produces a “rich” environment. Such a rich environment maybe achieved by providing a regeneration pulse, which is a sharp decreasein the air-to-fuel ratio for a short period of time. The term“recurrent” as used herein is meant to encompass both reductions in theoxygen concentration at regular intervals and reductions at randomintervals. The manner of effecting the decrease in oxygen concentrationand the extent of the decrease is well-known in the art.

The stored nitrates during the rich, or oxygen deficient, environmentare thermodynamically unstable, and thus are released by the adsorbent.The cobalt of the adsorbent also acts as a catalyst to catalyze areaction between the NO_(x) and the reducing species present in theexhaust gas, to produce N₂. Such a rich air-fuel ratio is usedperiodically as a regeneration pulse to assist in the regeneration ofthe LNT adsorbent. In the oxygen deficient environment present duringthe regeneration pulse, NO_(x) compounds released from the adsorbent arecatalytically reduced to N₂ upon contact with the catalyst in thepresence of carbon monoxide and residual hydrocarbons in the exhaustgas.

The adsorbent of the present invention comprises cobalt (Co) and analkali metal or alkaline earth metal, preferably potassium (K), and isloaded on an oxide support. The adsorbent of the present invention maybe in the form of an LNT. As is well known, the metals referred toherein actually exist within the adsorbent or other catalysts as oxides.In addition, it is believed that an adsorbent of the present inventionincluding cobalt and potassium form simple oxides, as opposed tocompound oxides. The phrase “loaded on” is used to cover all manners inwhich a catalytically or adsorpively active component (e.g., cobalt orpotassium) can be associated with an oxide, such as by being carried onthe oxide or ion-exchanged onto the oxide.

Any known high surface area oxide support may be used, and the specificsof the support do not appear to be critical for the present invention.Both natural and synthetic zeolites as well as acidic, basic or neutralzeolites may be used as catalyst support material. Further, the supportmaterial may also comprise metal oxides such as, but not limited to,zirconium oxide (ZrO₂) and aluminum oxide (Al₂O₃). Other supports suchas silica, titania, etc. may also be used. Preferred embodiments of thepresent invention incorporate ceria, or CeO₂, as the oxide support.

A preferred LNT for the present invention comprises cobalt and potassiumon a ceria support. The Co/alkali and/or alkaline earth metal mixturemay be binary or ternary. Binary mixtures include Co/K, Co/Cs, andCo/Ba. Examples of ternary mixtures include Co/K/Cs, Co/K/Ba, andCo/Cs/Ba. The relative amounts or the metals in the components willdepend on a number of factors including the metals used, the exhaustenvironment, and the desired properties of the adsorbent. In many cases,the binary metal oxide particles of Co/alkali metal may contain Co andan alkali metal in mole ratios of between 5:1 to 1:5. More preferably,the binary ratio is between 2:1 to 1:2.

The LNT of the present invention may additionally include one or moreplatinum group metals (PGMs) as part of the catalyst system, in additionto the cobalt and the alkali and/or alkaline earth metal group. Platinumgroup metals include platinum, palladium and rhodium or a combinationthereof. The amount of PGM to be used is well known in the art, however,a preferred weight percentage range would be from 0.01% to 5.0% of thetotal support material. In the present application, a PGM is notnecessary for conversion of the NO_(x) to N₂; however, it may beadvantageous in some cases. For example, a PGM may be employed toincrease low temperature activity or for higher thermal stability. TheLNT of the present invention, however, does not require the use of a PGMfor the conversion of NO_(x). Cobalt serves as an effective catalyst forthe reaction to take place between the nitrates and the reducing speciesin the exhaust gas to form nitrogen gas.

The present LNT composition can be used additionally with an upstreamcatalyst in an exhaust system, where the LNT of the present invention isplaced downstream from such catalysts. The upstream catalyst aids inachieving a greater reduction of nitrogen oxides, at least duringperiods of oxygen reduction. Conventionally known three-way catalysts(TWC), lean NO_(x) catalysts (LNC), or oxidation catalysts may be usedfor this purpose. As is well known, these upstream catalysts may performother functions, such as HC or CO reduction.

The composition of the present invention can be made and used in amanner consistent with conventional LNTs. The cobalt and alkali oralkaline earth metal components may be applied to a substrate orwashcoat, which are known in the art, as described in the followingexamples. The catalysts of the present invention, including Co/K aredeposited on the support material, either simultaneously orsequentially. As seen generally from examples which follow, thecomposition can be made by mixing Co or a salt thereof with K or a saltthereof, dissolving the mixture in water, then loading it onto an oxidesupport such as CeO₂. The resulting powder is then dried at temperaturesranging from 60° C. to 150° C., although preferably at 120° C. for 12hours. The dried powder is then calcined at temperatures ranging from400° C. to 600° C., preferably at 500° C. for 4 hours.

As will be described by the test procedure and examples which follow, Cowith preferably K or other alkali and/or alkaline earth metals resultsin higher NO_(x) conversion, even at high temperatures such as 350° C.to 500° C. Thus, an improved LNT catalyst is described by the presentinvention. The operating temperature depends on the adsorbent used.

EXAMPLES

A nitrogen oxide trap according to an embodiment of the presentinvention was prepared as follows. In a slurry impregnation method, asolution of 4.6 g of Co(NO₃)₂.6H₂O and 1.6 g of KNO₃ in 20 ml of waterwas added to a suspension of 10 g of CeO₂ in 50 ml of water. The mixturewas evaporated while being vigorously stirred until achieving a paste,which was dried in an oven for 24 hours at 120° C. The resulting powderwas calcined at 500° C. for 4 hours, then aged at 850° C. for 24 hoursin air.

The samples were tested in a laboratory powder reactor with a procedurethat consisted of a precondition followed by a lean-rich cycled test.0.1 g of material was loaded in the reactor and the sample was exposedto a constant total gas flow rate of 200 standard cm³/min.

The sample was preconditioned on ramp to 650° C., held for 15 minutes,cooled to 400° C., all under the rich conditions listed Table 1. Thetemperature was held at 400° C. and the cycle of 60 sec. lean/5 sec.rich for 20 cycles. Then the sample was cooled to 150° C. while cycling30 sec. lean/10 sec. rich.

After preconditioning, the LNT activity was measured at 150° C. byexposing the sample to 10 cycles at 120 sec. lean/5 sec. rich andcalculating NO_(x) conversions for each of the last 3 cycles. Theconversions for the 3 cycles were then averaged and reported as shown inFIG. 1. The LNT activity measurement was then repeated at 150, 225, 350,450, and 500° C.

TABLE 1 Gas Compositions GAS RICH LEAN NO 500 ppm 500 ppm CO₂  10% 10%O₂ — 12% CO 7.5% — H₂ 2.5% —

As seen from FIG. 1, the Co/K sample prepared by slurry impregnationmethod was compared with Mn/K supported on Ceo₂ and Pt/K supported onAl₂O₃. The Co/K LNT showed significantly higher percentage conversion ofthe NO_(x) at higher temperatures than the Mn/K and Pt/K. The followingTable 2 compares the results of the Test procedure:

TABLE 2 NO_(x) Conversion of 850° C. Aged Samples at SV = 25K with 120sec. lean/5 sec. rich 350° C. 450° C. 500° C.  9% Co/6% K 69% 80% 78%10% Mn/10% K 12% 33% 30%  1% Pt/6% K 32% 45% 37%

The present catalyst system shows higher LNT NO_(x) conversion activityin middle to high temperature ranges (i.e. 350-500° C.) compared toprevious adsorbent materials such as Ba, K, Cs, or Mn/K. Additionally,the Co/K material does not require a platinum group metal to convert NOto NO₂ for storage. The metal oxide-supported Mn/K system shows similarcharacteristics. As seen from FIG. 1, however, the Co/K system is moreactive and has a higher thermal durability than the Mn/K system. Afteraging at 850° C. for 24 hours in air, the Co/K system showedsubstantially better is LNT activity than the Mn/K system.

The following supplemental examples are representative, not limiting ofthe invention.

Example 1

In an incipient wetness impregnation method may also be used, 4.6 g ofCo(NO₃)₂.6H₂O and 1.6 g of KNO₃ (or 1.6 g of KOAc) were dissolved in 2.5ml of water. 10 g of CeO₂ was impregnated with the above solution viasequential or co-impregnation. The resulting powder was dried in an ovenfor 24 hours at 120° C., calcined at 500° C. for 4 hours, then aged at850° C. for 24 hours in air.

The NO_(x) conversion of Co/K supported on CeO₂ showed similaractivities at the same composition, regardless of the preparationmethod.

Example 2

A solution of 9.8 g of Co(NO₃)₂.6H₂O and 3.4 g of KNO₃ in 20 ml of waterwas added to a suspension of 20 g of CeO₂ in 50 ml of water. The mixturewas evaporated while being vigorously stirred until achieving a paste,which was dried in an oven for 24 h at 120° C. It was calcined at 500°C. for 4 hours and aged at 850° C. for 24 hours in air.

NO_(x) conversion (%) at 120 s lean/5 s rich cycles: 76% at 350° C., 81%at 450° C. and 75% at 500° C.

Example 3

3.11 g of Co(NO₃)₂.6H₂O was dissolved in 2.3 ml of water, and thenimpregnated onto 10 g of CeO₂. The powder was dried in an oven for 24hours at 120° C. and calcined at 500° C. for 4 hours. A 1.6 g of KNO₃was dissolved in 3.5 ml of water, and then impregnated onto the Co/CeO₂.The resulting powder was dried in an oven for 24 hours at 120° C. Thesample was calcined at 500° C. for 4 hours and aged at 850° C. for 24hours in air.

NO_(x) conversion (%) at 120 s lean/5 s rich cycles: 79% at 350° C., 84%at 450° C. and 76% at 500° C.

Example 4

4.69 g of Co(NO₃)₂.6H₂O was dissolved in 2.0 ml of water, and thenimpregnated onto 10 g of CeO₂. The powder was dried in an oven for 24hours at 120° C. then calcined at 500° C. for 4 hours. 1.1 g of KNO₃ wasdissolved in 3.5 ml of water, and then impregnated onto the Co/CeO₂. Theresulting powder was dried in an oven for 24 hours at 120° C., calcinedat 500° C. for 4 hours, and aged at 850° C. for 24 hours in air.

NO_(x) conversion (%) at 120 s lean/5 s rich cycles: 75% at 350° C., 82%at 450° C. and 76% at 500° C.

Example 5

3.11 g of Co(NO₃)₂.6H₂O was dissolved in 2.3 ml of water, and thenimpregnated onto 10 g of CeO₂. The powder was dried in an oven for 24hours at 120° C. and calcined at 500° C. for 4 hours. 1.1 g of KNO₃ wasdissolved in 3.5 ml of water, and then impregnated onto Co/CeO₂. Theresulting powder was dried in an oven for 24 hours at 120° C., calcinedat 500° C. for 4 hours and aged at 850° C. for 24 hours in air.

NO_(x) conversion (%) at 120 s lean/5 s rich cycles: 81% at 350° C., 85%at 450° C. and 79% at 500° C.

Example 6

A solution of 7.0 g of Co(NO₃)₂.6H₂O and 6.0 g of Ba(NO₃)₂ in 65 ml ofwater was added to a suspension of 20 g of CeO₂ in 50 ml of water. Themixture was evaporated while being vigorously stirred until achieving apaste, which was dried in an oven for 24 hours at 120° C. The sample wasthen calcined at 500° C. for 4 hours and aged at 850° C. for 24 hours inair.

NO_(x) conversion (%) at 120 s lean/5 s rich cycles: 20% at 350° C., 15%at 450° C. and 14% at 500° C.

Example 7

A 1.38 g of Co(NO₃)₂.6H₂O and 1.4 ml of Cs solution (436 g Cs/L) was isdissolved in 3.5 ml of water, and then impregnated onto 10 g of CeO₂.The powder was dried in an oven for 24 hours at 120° C., calcined at500° C. for 4 hours, then aged at 850° C. for 24 hours in air.

NO_(x) conversion (%) at 120 s lean/5 s rich cycles: 25% at 350° C., 19%at 450° C. and 18% at 500° C.

Example 8

A solution of 3.1 g of Co(NO₃)₂.6H₂O, 1.1 g of KNO₃ and 3.3 ml of Cssolution (436 g Cs/L) in 20 ml of water was added to a suspension of 20g of CeO₂ in 50 ml of water. The mixture was evaporated while beingvigorously stirred until achieving a paste, which was dried in an ovenfor 24 hours at 120° C., calcined at 500° C. for 4 hours, then aged at850° C. for 24 hours in air.

NO_(x) conversion (%) at 120 s lean/5 s rich cycles: 25% at 350° C., 48%at 450° C. and 46% at 500° C.

Example 1 was similar to the test procedure (uses same amount of Co/K),except an impregnation method was used. Examples 2-5 used differentratios of Co and K as the washcoat. Example 6 used the binary mixture ofCo and Ba.

Example 7 used Co and Cs. Example 8 used the ternary mixture of Co/K andCs. Resulting NO_(x) conversion of each example at varying temperaturesis listed in Table 3.

TABLE 3 NO_(x) conversion at 120 sec. lean/5 sec. rich cycles LNT 350°C. 450° C. 500° C. Test Co/K on CeO₂ 69% 80% 78% Procedure Example 1Co/K on CeO₂ 69% 80% 78% Example 2 Co/K on CeO₂ 76% 81% 75% Example 3 Kon Co/CeO₂ 79% 84% 76% Example 4 K on Co/CeO₂ 75% 82% 76% Example 5 K onCo/CeO₂ 81% 85% 79% Example 6 Co/Ba on CeO₂ 20% 15% 14% Example 7 Co/Cson CeO₂ 25% 19% 18% Example 8 Co/K/Cs on CeO₂ 25% 48% 46%

The results of the Examples for the present invention show a relativelyhigh NO_(x) conversion at the temperature range from 350° C. to 500° C.Example 6-example 8 have used Ba or Cs and have shown lower NO_(x)conversion than the previous use of K. As stated before, although otheralkali metals are contemplated for use with the present LNT, thepreferred alkali metal is K. These examples are merely representative ofthe present invention and are not limiting in any way.

Although illustrated and described herein with reference to certainspecific embodiments and examples, the present invention is neverthelessnot intended to be limited to the details shown. Rather, variousmodifications may be made in the details within the scope and range ofequivalents of the claims and without departing from the spirit of theinvention.

1. A composition which adsorbs nitrogen oxides present in exhaust gasesproduced by an engine during lean-burn conditions, said compositioncomprising: an oxide support; and at least two components loaded on saidsupport and comprising cobalt and at least one alkali metal or alkalineearth metal.
 2. The composition of claim 1, wherein said at least onealkali metal or alkaline earth metal comprises at least one of cesiumand barium.
 3. The composition of claim 1, wherein said cobalt and atleast one alkali metal or alkaline earth metal are a ternary mixture. 4.The composition of claim 3, wherein said at least one alkali metal oralkaline earth metal is selected from the group consisting of potassiumand cesium, potassium and barium, and cesium and barium.
 5. Thecomposition of claim 1, wherein said at least two components furthercomprise a platinum group metal.
 6. A process for converting nitrogenoxides present in exhaust gas produced by an engine, said processcomprising: contacting said exhaust gas containing nitrogen oxides withan adsorbent comprising: an oxide support; and at least two componentsloaded on said support and comprising cobalt and at least one alkalimetal or alkaline earth metal, wherein said nitrogen oxides are adsorbedby said adsorbent in lean-burn conditions; and recurrently reducingoxygen concentration of said exhaust gas to cause desorption of saidnitrogen oxides from said adsorbent and reduction of said nitrogenoxides to nitrogen.
 7. The process of claim 6, wherein said at least onealkali metal or alkaline earth metal comprises potassium.
 8. The processof claim 6, wherein said at least two components further comprise aplatinum group metal.
 9. An exhaust system for converting nitrogenoxides present in exhaust gas produced by an engine, said exhaust systemcomprising: an upstream catalyst capable of reducing nitrogen oxides;and a downstream lean NOx trap composition comprising an oxide supportand at least two components comprising cobalt and at least one alkalimetal or alkaline earth metal, said components loaded on said oxidesupport.
 10. The exhaust system of claim 9, wherein said upstreamcatalyst is selected from the group consisting of a three way catalyst,a lean NOx catalyst, and an oxidation catalyst.
 11. The exhaust systemof claim 9, wherein said at least one alkali or alkaline earth metal isselected from the group consisting of potassium, cesium, and barium. 12.The exhaust system of claim 9, wherein said at least two componentscomprise said cobalt and said at least one alkali or alkaline earthmetal in a mole ratio of between 5:1 to 1:5.
 13. The exhaust system ofclaim 9, wherein said oxide support comprises ceria.
 14. The exhaustsystem of claim 9, wherein said lean NOx trap composition furthercomprises a platinum group metal.
 15. The exhaust system of claim 9,wherein said lean NOx trap composition further comprises rhodium. 16.The exhaust system of claim 9, wherein said oxide support consists ofceria.
 17. The exhaust system of claim 9, wherein said at least onealkali metal or alkaline earth metal comprises potassium.
 18. Theexhaust system of claim 17, wherein said cobalt is in the form of cobaltoxide and said potassium is in the form of potassium oxide.
 19. Theexhaust system of claim 18, wherein said cobalt oxide and said potassiumoxide are in the form of simple oxides.